Assessment of physical/mechanical properties and cytotoxicity of dual-cured resin cements containing Sr-bioactive glass nanoparticles and calcium phosphate.

The aim was to develop dual-cured resin cements containing Sr-bioactive glass nanoparticles (Sr-BGNPs; 5 or 10 wt%) and monocalcium phosphate monohydrate (MCPM; 3 or 6 wt%). Effects of additives on degree of monomer conversion (DC), biaxial flexural strength/modulus, shear bond strength (SBS), mass/volume change, color stability, ion release, and cytotoxicity were examined. Controls included material without reactive fillers and Panavia SA Plus (PV). Experimental cements showed higher DC than PV regardless of light activation (p<0.05). Mean SBS and color stability were comparable between experimental cements and PV. Cell viability upon the exposure to sample extracts of experimental cements was 80%-92%. High additive concentrations led to lower strength and modulus than PV (p<0.05). The additives increased mass change, reduced color stability, and promoted ion release. The experimental resin cements demonstrated acceptable mechanical/chemical properties and cytotoxicity. The additives reduced the strength but provided ion release, a desirable action to prevent recurrent caries.

Modifying dental composites to formulate novel methacrylate-based bone cements with improved polymerisation kinetics, and mechanical properties.

OBJECTIVES: The aim was to develop bone composites with similar working times, faster polymerisation and higher final conversion in comparison to Cortoss™. Additionally, low shrinkage/heat generation and improved short and longer-term mechanical properties are desirable. METHODS: Four urethane dimethacrylate based composites were prepared using tri-ethylene-glycol dimethacrylate (TEGDMA) or polypropylene dimethacrylate (PPGDMA) diluent and 0 or 20 wt% fibres in the glass filler particles. FTIR was used to determine reaction kinetics, final degrees of conversions, and polymerisation shrinkage/heat generation at 37 °C. Biaxial flexural strength, Young's modulus and compressive strength were evaluated after 1 or 30 days in water. RESULTS: Experimental materials all had similar inhibition times to Cortoss™ (140 s) but subsequent maximum polymerisation rate was more than doubled. Average experimental composite final conversion (76%) was higher than that of Cortoss™ (58%) but with less heat generation and shrinkage. Replacement of TEGDMA by PPGDMA gave higher polymerisation rates and conversions while reducing shrinkage. Early and aged flexural strengths of Cortoss™ were 93 and 45 MPa respectively. Corresponding compressive strengths were 164 and 99 MPa. Early and lagged experimental composite flexural strengths were 164-186 and 240-274 MPa whilst compressive strengths were 240-274 MPa and 226-261 MPa. Young's modulus for Cortoss™ was 3.3 and 2.2 GPa at 1 day and 1 month. Experimental material values were 3.4-4.8 and 3.0-4.1 GPa, respectively. PPGDMA and fibres marginally reduced strength but caused greater reduction in modulus. Fibres also made the composites quasi-ductile instead of brittle. SIGNIFICANCE: The improved setting and higher strengths of the experimental materials compared to Cortoss™, could reduce monomer leakage from the injection site and material fracture, respectively. Lowering modulus may reduce stress shielding whilst quasi-ductile properties may improve fracture tolerance. The modified dental composites could therefore be a promising approach for future bone cements.

Assessment of Mechanical/Chemical Properties and Cytotoxicity of Resin-Modified Glass Ionomer Cements Containing Sr/F-Bioactive Glass Nanoparticles and Methacrylate Functionalized Polyacids.

This study prepared low-toxicity, elemental-releasing resin-modified glass ionomer cements (RMGICs). The effect of 2-hydroxyethyl methacrylate (HEMA, 0 or 5 wt%) and Sr/F-bioactive glass nanoparticles (Sr/F-BGNPs, 5 or 10 wt%) on chemical/mechanical properties and cytotoxicity were examined. Commercial RMGIC (Vitrebond, VB) and calcium silicate cement (Theracal LC, TC) were used as comparisons. Adding HEMA and increasing Sr/F-BGNPs concentration decreased monomer conversion and enhanced elemental release but without significant effect on cytotoxicity. Rising Sr/F-BGNPs reduced the strength of the materials. The degree of monomer conversion of VB (96%) was much higher than that of the experimental RMGICs (21-51%) and TC (28%). The highest biaxial flexural strength of experimental materials (31 MPa) was significantly lower than VB (46 MPa) (p < 0.01) but higher than TC (24 MPa). The RMGICs with 5 wt% HEMA showed higher cumulative fluoride release (137 ppm) than VB (88 ppm) (p < 0.01). Unlike VB, all experimental RMGICs showed Ca, P, and Sr release. Cell viability in the presence of extracts from experimental RMGICs (89-98%) and TC (93%) was significantly higher than for VB (4%). Experimental RMGICs showed desirable physical/mechanical properties with lower toxicity than the commercial material.

Effects of Novel Dental Composites on Streptococcus mutans Biofilms.

With the phase-out of amalgam and the increase in minimally invasive dentistry, there is a growing need for high-strength composite materials that can kill residual bacteria and promote tooth remineralization. This study quantifies how antibacterial polylysine (PLS) and re-mineralizing monocalcium phosphate monohydrate (MCPM) affect Streptococcus mutans biofilms and the strength of dental composites. For antibacterial studies, the MCPM-PLS filler percentages were 0-0, 8-4, 12-6, and 16-8 wt% of the composite filler phase. Composite discs were immersed in 0.1% sucrose-supplemented broth containing Streptococcus mutans (UA159) and incubated in an anaerobic chamber for 48 h. Surface biomass was determined by crystal violet (CV) staining. Growth medium pH was measured at 24 and 48 h. Biofilm bacterial viability (CFU), exo-polysaccharide (water-soluble glucan (WSG) and water-insoluble glucan (WIG)), and extracellular DNA (eDNA) were quantified. This was by serial dilution plate counting, phenol-sulfuric acid microassay, and fluorometry, respectively. The biaxial flexural strengths were determined after water immersion for 1 week, 1 month, and 1 year. The MCPM-PLS wt% were 8-4, 8-8, 16-4 and 16-8. The normalized biomass, WSG, and WIG showed a linear decline of 66%, 64%, and 55%, respectively, as the PLS level increased up to 8%. The surrounding media pH (4.6) was all similar. A decrease in bacterial numbers with the 12-6 formula and a significant reduction with 16-8 compared to the 0-0 formulation was observed. The eDNA concentrations in biofilms formed on 12-6 and 16-8 formulations were significantly less than the 0-0 control and 8-4 formulations. Doubling MCPM and PLS caused a 14 and 19% reduction in strength in 1 week, respectively. Average results were lower at 1 month and 1 year but affected less upon doubling MCPM and PLS levels. Moreover, a 4% PLS may help to reduce total biomass and glucan levels in biofilms on the above composites. Higher levels are required to reduce eDNA and provide bactericidal action, but these can decrease early strength.

Assessment of Physical/Mechanical Performance of Dental Resin Sealants Containing Sr-Bioactive Glass Nanoparticles and Calcium Phosphate.

The aim of this study was to assess the chemical/mechanical properties of ion-releasing dental sealants containing strontium-bioactive glass nanoparticles (Sr-BGNPs) and monocalcium phosphate monohydrate (MCPM). Two experimental sealants, TS1 (10 wt% Sr-BGNPs and 2 wt% MCPM) and TS2 (5 wt% Sr-BGNPs and 4 wt% MCPM), were prepared. Commercial controls were ClinproXT (CP) and BeautiSealant (BT). The monomer conversion (DC) was tested using ATR−FTIR (n = 5). The biaxial flexural strength (BFS) and modulus (BFM) were determined (n = 5) following 24 h and 7 days of immersion in water. The Vickers surface microhardness (SH) after 1 day in acetic acid (conc) versus water was tested (n = 5). The bulk and surface calcium phosphate precipitation in simulated body fluid was examined under SEM-EDX. The ion release at 4 weeks was analyzed using ICP-MS (n = 5). The DC after 40 s of light exposure of TS1 (43%) and TS2 (46%) was significantly lower than that of CP (58%) and BT (61%) (p < 0.05). The average BFS of TS1 (103 MPa), TS2 (123 MPa), and BT (94 MPa) were lower than that of CP (173 MPa). The average BFM and SH of TS1 (2.2 GPa, 19 VHN) and TS2 (2.0 GPa, 16 VHN) were higher than that of CP (1.6 GPa, 11 VHN) and BT (1.3 GPa, 12 VHN). TS1 showed higher Ca, P, and Sr release than TS2. Bulk calcium phosphate precipitation was detected on TS1 and TS2 suggesting some ion exchange. In conclusion, the DC of experimental sealants was lower than that of commercial materials, but their mechanical properties were within the acceptable ranges. The released ions may support remineralizing actions.

Renewal MI Dental Composite Etch and Seal Properties.

This study's aim was to assess whether the Renewal MI composite can self-etch enamel, seal sound cavities, and stabilize demineralized dentine. Etching was assessed using scanning electron microscopy (SEM). Cavity sealing was quantified using the ISO-11405 dye microleakage test. Demineralized dentine stabilization was evaluated by visualizing resin tag formation, enzyme activity and mineral precipitation at the adhesion interface. Renewal MI provided a mild etching of sound enamel in comparison with 37% phosphoric acid. It provided a comparable seal of sound cavities to Z250/Scotchbond Universal adhesive and a superior seal to Activa, Fuji IX and Fuji II LC. With demineralized dentine, Renewal MI formed 300-400 µm resin tags covering 63% of the adhesion interface compared with 55 and 39% for Z250/Scotchbond and Activa. Fuji IX and Fuji II LC formed no resin tags. A higher tag percentage correlated with lower surface enzyme activity. Unlike Activa and Fuji II LC, Renewal MI promoted mineral precipitation from simulated body fluid, occluding adjacent dentinal tubules within 6 months. These novel etching and sealing properties may facilitate Renewal MI's application in minimally invasive dentistry.

Determination of Dental Adhesive Composition throughout Solvent Drying and Polymerization Using ATR-FTIR Spectroscopy.

The of this study aim was to develop a rapid method to determine the chemical composition, solvent evaporation rates, and polymerization kinetics of dental adhesives. Single-component, acetone-containing adhesives One-Step (OS; Bisco, Anaheim, CA, USA), Optibond Universal (OU; Kerr, Brea, CA, USA), and G-Bond (GB; GC, Tokyo, Japan) were studied. Filler levels were determined gravimetrically. Monomers and solvents were quantified by comparing their pure Attenuated Total Reflectance-Fourier Transform Infra-Red (ATR-FTIR) spectra, summed in different ratios, with those of the adhesives. Spectral changes at 37 °C, throughout passive evaporation for 5 min, then polymerisation initiated by 20 s, and blue light emitting diode (LED) (600 mW/cm2) exposure (n = 3) were determined. Evaporation and polymerisation extent versus time and final changes were calculated using acetone (1360 cm-1) and methacrylate (1320 cm-1) peaks. OS, OU, and GB filler contents were 0, 9.6, and 5.3%. FTIR suggested OS and OU were Bis-GMA based, GB was urethane dimethacrylate (UDMA) based, and that each had a different diluent and acidic monomers and possible UDMA/acetone interactions. Furthermore, initial acetone percentages were all 40-50%. After 5 min drying, they were 0% for OS and OU but 10% for GB. Whilst OS had no water, that in OU declined from 18 to 10% and in GB from 25 to 20% upon drying. Evaporation extents were 50% of final levels at 23, 25, and 113 s for OS, OU, and GB, respectively. Polymerisation extents were all 50 and 80% of final levels before 10 and at 20 s of light exposure, respectively. Final monomer polymerisation levels were 68, 69, and 88% for OS, OU, and GB, respectively. An appreciation of initial and final adhesive chemistry is important for understanding the properties. The rates of evaporation and polymerisation provide indications of relative required drying and light cure times. UDMA/acetone interactions might explain the considerably greater drying time of GB.

Varying 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) level improves polymerisation kinetics and flexural strength in self-adhesive, remineralising composites.

OBJECTIVES: To assess the influence of systematically varying concentrations of 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) versus 3% 4-META on the polymerisation kinetics and shrinkage, biaxial flexural strength (BFS) and modulus of remineralising composites. METHODS: Composites were prepared by adding poly(propylene glycol) dimethacrylate (24 wt%), camphorquinone (1 wt%) and MDP (0%, 5%, 10%, 15% and 20 wt%) or 4-META (3%) to urethane dimethacrylate. These were mixed with glass fillers containing 8 wt% monocalcium phosphate and 4 wt% polylysine (powder-liquid ratio of 3:1). Continuous spectral changes, following 20 s light exposure (37 °C), were assessed with an ATR-FTIR to monitor polymerisation kinetics (n = 3). Final extrapolated conversions (DC,max) were employed to calculate polymerisation shrinkage. BFS and modulus of 24-h dry stored disc specimens (10 × 1 mm; n = 10) were determined using a ball-on-ring jig setup. RESULTS: Maximum rate of polymerisation and DC,max increased linearly from 2.5 to 3.5% s-1 and 67 to 83%, respectively, upon increasing MDP from 0 to 20 wt%. Values with 3% 4-META were 2.6% s-1 and 78%. Shrinkage was 3.8 ± 0.3% for all formulations. Raising 4-META or MDP from 0 to 3 versus 5%, respectively, increased strength from 106 to 145 versus 136 MPa. A decreasing trend with higher MDP concentrations was noted. Elastic modulus showed no specific trend upon MDP increase. SIGNIFICANCE: Whilst final conversion levels were enhanced by 3% 4-META or >5% MDP, trends did not correlate with strength. Peak strengths with 3% 4-META or 5% MDP may therefore be due to acidic monomers providing linkage between the hydrophilic, non-silane treated particles and the polymer matrix.

Methacrylate peak determination and selection recommendations using ATR-FTIR to investigate polymerisation of dental methacrylate mixtures.

Investigation of polymerisation kinetics using ATR-FTIR systems is common in many dental studies. However, peak selection methods to calculate monomer-polymer conversion can vary, consequently affecting final results. Thus, the aim of this study is to experimentally confirm which method is less prone to systematic errors. Three commercial restorative materials were tested-Vertise Flow (VF), Constic and Activa Bioactive Restorative Kids. Firstly, Attenuated Total Reflectance Fourier Transform Infra-Red (ATR-FTIR) (Spectrum One, Perkin-Elmer, UK) spectra of monomers were acquired-10-methacryloyloxy decyl dihydrogen phosphate (10-MDP), bisphenol-A glycidyl dimethacrylate (Bis-GMA), 2-hydroxyethyl methacrylate (HEMA), triethyelene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA) to investigate proportionality of methacrylate peak heights versus concentration. Spectral changes upon light exposure of 2 mm discs of the restorative materials (irradiated for 20 s, LED curing unit 1100-1330 mW/cm2) were assessed to study polymerisation kinetics (n = 3), with continuous acquisition of spectra, before, during and after light exposure. Peak differences and degrees of conversion (DC %) were calculated using 1320/1336, 1320/1350 and 1636/1648 cm-1 as reaction/reference peaks. Inferential statistics included a MANOVA and within-subjects repeated measures ANOVA design (5% significance level). Proportionality of methacrylate peak height to concentration was confirmed, with the 1320/1352 cm-1 peak combination showing the lowest coefficient of variation (8%). Difference spectra of the polymerisation reaction showed noise interference around the 1500-1800 cm-1 region. Across the different materials, DC % results are highly dependent upon peak selection (p<0.001), with higher variability associated to the 1636 cm-1. Significant differences in the materials were only detected when the 1320 cm-1 peak was used (p<0.05). Within the same materials, methods were significantly different for Constic and Activa (p<0.05). It is possible to conclude that the 1320 cm-1 peak is more adequate to assess polymerisation of methacrylates and is therefore recommended.

Modelling ATR-FTIR Spectra of Dental Bonding Systems to Investigate Composition and Polymerisation Kinetics.

Component ratios and kinetics are key to understanding and optimising novel formulations. This warrants investigation of valid methods. Attenuated Total Reflectance Fourier Transform Infra-Red (ATR)-FTIR spectra of separate primers/adhesives were modelled using summed spectra of solvents (water, ethanol), methacrylate monomers (HEMA (hydroxyethyl methacrylate), Bis-GMA (bisphenol A glycidyl methacrylate), and 10-MDP (10-methacryloyloxydecyl dihydrogen phosphate)), and fillers, multiplied by varying fractions. Filler loads were obtained following their separation from the adhesives, by analysing three repetitions (n = 3). Spectral changes during light exposure at 37 °C (20 s, LED 1100-1330 mW/cm2) were used to determine polymerisation kinetics (n = 3). Independent samples T-test was used for statistical analysis (significance level of 5%). FTIR modelling suggested a primer solvent percentage of OBFL (Optibond FL) (30%) was half that of CFSE (Clearfil SE 2) (60%). OBFL included ethanol and water, while CFSE included only water. Monomer peaks were largely those of HEMA with lower levels of phosphate monomers. OBFL/CFSE adhesive model spectra suggested that both contained equal volumes of Bis-GMA/HEMA, with CFSE having 10-MDP. Filler levels and spectra from OBFL (48 wt.%) and CFSE (5 wt.%) were different. Both systems reached a 50% conversion rate within seconds of light exposure. The final conversion for OBFL (74 ± 1%) was lower compared to CFSE (79 ± 2%) (p < 0.05). ATR-FTIR is a useful method to investigate relative levels of main components in bonding systems and their polymerisation kinetics. Such information is valuable to understanding such behaviour.

Effect of Novel Antibacterial Composites on Bacterial Biofilms.

Continuing cariogenic bacterial growth demineralizing dentine beneath a composite filling is the most common cause of tooth restoration failure. Novel composites with antibacterial polylysine (PLS) (0, 4, 6, or 8 wt%) in its filler phase were therefore produced. Remineralising monocalcium phosphate was also included at double the PLS weight. Antibacterial studies involved set composite disc placement in 1% sucrose-supplemented broth containing Streptococcus mutans (UA159). Relative surface bacterial biofilm mass (n = 4) after 24 h was determined by crystal violet-binding. Live/dead bacteria and biofilm thickness (n = 3) were assessed using confocal laser scanning microscopy (CLSM). To understand results and model possible in vivo benefits, cumulative PLS release from discs into water (n = 3) was determined by a ninhydrin assay. Results showed biofilm mass and thickness decreased linearly by 28% and 33%, respectively, upon increasing PLS from 0% to 8%. With 4, 6, and 8 wt% PLS, respectively, biofilm dead bacterial percentages and PLS release at 24 h were 20%, 60%, and 80% and 85, 163, and 241 µg/disc. Furthermore, initial PLS release was proportional to the square root of time and levelled after 1, 2, and 3 months at 13%, 28%, and 42%. This suggested diffusion controlled release from water-exposed composite surface layers of 65, 140, and 210 µm thickness, respectively. In conclusion, increasing PLS release initially in any gaps under the restoration to kill residual bacteria or longer-term following composite/tooth interface damage might help prevent recurrent caries.

Early Polylysine Release from Dental Composites and Its Effects on Planktonic Streptococcus mutans Growth.

The study aim was to assess the effect of incorporating polylysine (PLS) filler at different mass fractions (0.5, 1 and 2 wt%) on PLS release and Streptococcus mutans planktonic growth. Composite containing PLS mass and volume change and PLS release upon water immersion were assessed gravimetrically and via high-performance liquid chromatography (HPLC), respectively. Disc effects on bacterial counts in broth initially containing 8 × 105 versus 8 × 106 CFU/mL Streptococcus mutans UA159 were determined after 24 h. Survival of sedimented bacteria after 72 h was determined following LIVE/DEAD staining of composite surfaces using confocal microscopy. Water sorption-induced mass change at two months increased from 0.7 to 1.7% with increasing PLS concentration. Average volume increases were 2.3% at two months whilst polylysine release levelled at 4% at 3 weeks irrespective of composite PLS level. Early percentage PLS release, however, was faster with higher composite content. With 0.5, 1 and 2% polylysine initially in the composite filler phase, 24-h PLS release into 1 mL of water yielded 8, 25 and 93 ppm respectively. With initial bacterial counts of 8 × 105 CFU/mL, this PLS release reduced 24-h bacterial counts from 109 down to 108, 107 and 102 CFU/mL respectively. With a high initial inoculum, 24-h bacterial counts were 109 with 0, 0.5 or 1% PLS and 107 with 2% PLS. As the PLS composite content was raised, the ratio of dead to live sedimented bacteria increased. The antibacterial action of the experimental composites could reduce residual bacteria remaining following minimally invasive tooth restorations.

Demineralization-remineralization dynamics in teeth and bone.

Biomineralization is a dynamic, complex, lifelong process by which living organisms control precipitations of inorganic nanocrystals within organic matrices to form unique hybrid biological tissues, for example, enamel, dentin, cementum, and bone. Understanding the process of mineral deposition is important for the development of treatments for mineralization-related diseases and also for the innovation and development of scaffolds. This review provides a thorough overview of the up-to-date information on the theories describing the possible mechanisms and the factors implicated as agonists and antagonists of mineralization. Then, the role of calcium and phosphate ions in the maintenance of teeth and bone health is described. Throughout the life, teeth and bone are at risk of demineralization, with particular emphasis on teeth, due to their anatomical arrangement and location. Teeth are exposed to food, drink, and the microbiota of the mouth; therefore, they have developed a high resistance to localized demineralization that is unmatched by bone. The mechanisms by which demineralization-remineralization process occurs in both teeth and bone and the new therapies/technologies that reverse demineralization or boost remineralization are also scrupulously discussed. Technologies discussed include composites with nano- and micron-sized inorganic minerals that can mimic mechanical properties of the tooth and bone in addition to promoting more natural repair of surrounding tissues. Turning these new technologies to products and practices would improve health care worldwide.

Poly(propylene glycol) and urethane dimethacrylates improve conversion of dental composites and reveal complexity of cytocompatibility testing.

OBJECTIVES: To determine the effects of various monomers on conversion and cytocompatibility of dental composites and to improve these properties without detrimentally affecting mechanical properties, depth of cure and shrinkage. METHODS: Composites containing urethane dimethacrylate (UDMA) or bisphenol A glycidyl methacrylate (Bis-GMA) with poly(propylene glycol) dimethacrylate (PPGDMA) or triethylene glycol dimethacrylate (TEGDMA) were characterized using the following techniques: conversion (FTIR at 1 and 4mm depths), depth of cure (BS EN ISO 4049:2009 and FTIR), shrinkage (BS EN ISO 17304:2013 and FTIR), strength and modulus (biaxial flexural test) and water sorption. Cytocompatibility of composites and their liquid phase components was assessed using three assays (resazurin, WST-8 and MTS). RESULTS: UDMA significantly improved conversion, BFS and depth of cure compared to Bis-GMA, without increasing shrinkage. UDMA was cytotoxic at lower concentrations than Bis-GMA, but extracts of Bis-GMA-containing composites were less cytocompatible than of those containing UDMA. PPGDMA improved conversion and depth of cure compared to TEGDMA, without detrimentally affecting shrinkage. TEGDMA was shown by all assays to be highly toxic. Resazurin, but not WST-8 and MTS, suggested that PPGDMA exhibited improved cytocompatibility compared to TEGDMA. SIGNIFICANCE: The use of UDMA and PPGDMA results in composites with excellent conversion, depth of cure and mechanical properties, without increasing shrinkage. Composites containing UDMA appear to be slightly more cytocompatible than those containing Bis-GMA. These monomers may therefore improve the material properties of dental restorations, particularly bulk fill materials. The effect of diluent monomer on cytocompatibility requires further investigation.

Development of dental composites with reactive fillers that promote precipitation of antibacterial-hydroxyapatite layers.

The study aim was to develop light-curable, high strength dental composites that would release calcium phosphate and chlorhexidine (CHX) but additionally promote surface hydroxyapatite/CHX co-precipitation in simulated body fluid (SBF). 80 wt.% urethane dimethacrylate based liquid was mixed with glass fillers containing 10 wt.% CHX and 0, 10, 20 or 40 wt.% reactive mono- and tricalcium phosphate (CaP). Surface hydroxyapatite layer thickness/coverage from SEM images, Ca/Si ratio from EDX and hydroxyapatite Raman peak intensities were all proportional to both time in SBF and CaP wt.% in the filler. Hydroxyapatite was, however, difficult to detect by XRD until 4 weeks. XRD peak width and SEM images suggested this was due to the very small size (~10 nm) of the hydroxyapatite crystallites. Precipitate mass at 12 weeks was 22 wt.% of the sample CaP total mass irrespective of CaP wt.% and up to 7 wt.% of the specimen. Early diffusion controlled CHX release, assessed by UV spectrometry, was proportional to CaP and twice as fast in water compared with SBF. After 1 week, CHX continued to diffuse into water but in SBF, became entrapped within the precipitating hydroxyapatite layer. At 12 weeks CHX formed 5 to 15% of the HA layer with 10 to 40 wt.% CaP respectively. Despite linear decline of strength and modulus in 4 weeks from 160 to 101 MPa and 4 to 2.4 GPa, respectively, upon raising CaP content, all values were still within the range expected for commercial composites. The high strength, hydroxyapatite precipitation and surface antibacterial accumulation should reduce tooth restoration failure due to fracture, aid demineralised dentine repair and prevent subsurface carious disease respectively.

Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol-gel method: dissolution behaviour and biological properties after crystallisation.

Hydroxyapatite (HA), fluor-hydroxyapatite (FHA) with varying levels of fluoride ion substitution and fluorapatite (FA) were synthesised by the sol-gel method as possible implant coating or bone-grafting materials. Calcium nitrate and triethyl phosphite were used as precursors under an ethanol-water based solution. Different amounts of ammonium fluoride were incorporated for the preparation of the FHA and FA sol-gels. After heating and powdering the sol-gels, dissolution behaviour was assessed using ion chromatography to measure Ca(2+) and PO4 (3-) ion release. Biological behaviour was assessed using cellular proliferation with human osteosarcoma cells and alamarBlue™ assay. Statistical analysis was performed with a two way analysis of variance and post hoc testing with a Bonferroni correction. Increasing fluoride substitution into an apatite structure decreased the dissolution rate. Increasing the firing temperature of the HA, FHA and FA sol-gels up to 1,000 °C decreased the dissolution rate. There was significantly higher cellular proliferation on highly substituted FHA and FA than on HA or Titanium. The properties of an implant coating or bone grafting material can be tailored to meet specific requirements by altering the amount of fluoride that is incorporated into the original apatite structure. The dissolution behaviour can further be altered by the temperature at which the sol-gel is fired.

High strength re-mineralizing, antibacterial dental composites with reactive calcium phosphates.

OBJECTIVE: Development of high strength dental composites with adhesive, antibacterial and re-mineralizing potential. MATERIALS: Urethane and triethylene glycol dimethacrylates were combined with HEMA (10 or 20wt%) and 2MP (2 or 10wt%), antibacterial chlorhexidine (2.5wt%) and chemical cure initiators. Reactive mono/tri calcium phosphate (CP) mixed with silica/silicon carbide nanoparticles (S) (CP:S weight ratio 1:2 or 2:1) was added (50wt%). RESULTS: Decreasing CP/S ratio and HEMA content reduced monomer conversion at 15min from 93 to 63%. Conversely, decreasing CP/S increased initial "dry" compressive (137-203MPa) and flexural (79-116MPa) strength. With high HEMA content, these decreased by ∼15-20MPa upon 24h water storage. With low HEMA content, average decline was <8MPa due to reduced water sorption. Early water sorption induced mass increase, volume expansion, mono calcium phosphate dissolution and chlorhexidine release, were proportional to the initial calcium phosphate content. Furthermore, they increased ∼1.5 fold upon raising HEMA wt%. These diffusion controlled processes and strength decline slowed after 24h as phosphates reaction bound water within the materials. Increasing 2MP concentration reduced calcium release but did not affect strength. Formulations with high CP/S indicated greater antibacterial activity in agar diffusion and in vitro biofilm tests. SIGNIFICANCE: New material use beneath a conventional composite could potentially reduce high failure rates associated with residual caries and bacterial microleakage.

Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol-gel method. Optimisation, characterisation and rheology.

OBJECTIVES: Currently, most titanium implant coatings are made using hydroxyapatite and a plasma spraying technique. There are however limitations associated with plasma spraying processes including poor adherence, high porosity and cost. An alternative method utilising the sol-gel technique offers many potential advantages but is currently lacking research data for this application. It was the objective of this study to characterise and optimise the production of Hydroxyapatite (HA), fluorhydroxyapatite (FHA) and fluorapatite (FA) using a sol-gel technique and assess the rheological properties of these materials. METHODS: HA, FHA and FA were synthesised by a sol-gel method. Calcium nitrate and triethylphosphite were used as precursors under an ethanol-water based solution. Different amounts of ammonium fluoride (NH4F) were incorporated for the preparation of the sol-gel derived FHA and FA. Optimisation of the chemistry and subsequent characterisation of the sol-gel derived materials was carried out using X-ray Diffraction (XRD) and Differential Thermal Analysis (DTA). Rheology of the sol-gels was investigated using a viscometer and contact angle measurement. RESULTS: A protocol was established that allowed synthesis of HA, FHA and FA that were at least 99% phase pure. The more fluoride incorporated into the apatite structure; the lower the crystallisation temperature, the smaller the unit cell size (changes in the a-axis), the higher the viscosity and contact angle of the sol-gel derived apatite. SIGNIFICANCE: A technique has been developed for the production of HA, FHA and FA by the sol-gel technique. Increasing fluoride substitution in the apatite structure alters the potential coating properties.

Viscoelastic and biological performance of low-modulus, reactive calcium phosphate-filled, degradable, polymeric bone adhesives.

The aim of this study was to investigate the effect of reactive mono- and tricalcium phosphate addition on the mechanical, surface free energy, degradation and cell compatibility properties of poly(lactide-co-propylene glycol-co-lactide) dimethacrylate (PPGLDMA) thin films. Dry composites containing up to 70 wt.% filler were in a flexible rubber state at body temperature. Filler addition increased the initial strength and Young's modulus and reduced the elastic and permanent deformation under load. The polymer had high polar surface free energy, which might enable greater spread upon bone. This was significantly reduced by filler addition but not by water immersion for 7 days. The samples exhibited reduced water sorption and associated bulk degradation when compared with previous work with thicker samples. Their cell compatibility was also improved. Filler raised water sorption and degradation but improved cell proliferation. The materials are promising bone adhesive candidates for low-load-bearing areas.

Reactive calcium-phosphate-containing poly(ester-co-ether) methacrylate bone adhesives: setting, degradation and drug release considerations.

This study has investigated novel bone adhesives consisting of fluid photo-polymerizable poly(lactide-co-propylene glycol-co-lactide)dimethacrylate (PGLA-DMA) mixed with systematically varying fillers of ß-tricalcium phosphate (ß-TCP) and monocalcium phosphate monohydrate (MCPM), for the delivery of an antibacterial drug chlorhexidine (CHX). All formulations were found to polymerize fully within 200 s after exposure to blue light. In addition, water sorption by the polymerized materials catalyzed varying filler conversion to dicalcium phosphate (DCP) (i.e. brushite and monetite). With greater DCP levels, faster degradation was observed. Moreover, increase in total filler content enhanced CHX release, associated with higher antibacterial activity. These findings thus suggest that such rapid-setting and degradable adhesives with controllable drug delivery property could have potential clinical value as bone adhesives with antibacterial activity.